Silated core polysulfides, their preparation and use in filled elastomer compositions

Abstract

This invention relates to novel sulfur-containing silane coupling agents, and organic polymers containing carbon-carbon double bonds. These novel silanes can be carried on organic and inorganic fillers. The invention also relates to articles of manufacture, particularly tires, made from the elastomer compositions described herein.

1. A silated core polysulfide of the general formula
   [Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p    
 
       wherein:
 each occurrence of G 1  is independently selected from a polyvalent hydrocarbon-containing species having from 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of G 2  is independently selected from a polyvalent hydrocarbon-containing species of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of R 1  and R 3  is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms; 
 each occurrence of Y 1  and Y 2  is independently selected from the group consisting of silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of R 2  is a chemical bond or a straight chain hydrocarbon represented by —(CH 2 ) f —; 
 each occurrence of X 1  is independently selected from the group consisting of —Cl, —Br, —OH, OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of X 2  and X 3  is independently selected from the group consisting of hydrogen, R 6 , wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, X 1 , wherein X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and —OSi containing groups that result from the condensation of silanols; 
 each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given wherein a, c and e are 1 to about 3; b is 1 to about 5; d is 1 to about 5; f is 1 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10; and, 
 each occurrence of R 4  and R 5  is independently selected from a polyvalent heterocarbon fragment having from 1 to 27 carbon atoms. 
 
     
     
       2. The silated core polysulfide of  claim 1 
 wherein the heteroatom of R 4  and R 5  is selected from the group consisting of sulfur, oxygen, nitrogen, and mixtures thereof. 
 
     
     
       3. The silated core polysulfide of  claim 1  wherein the value of x is from 2 to 4. 
     
     
       4. A silated core polysulfide of the general formula
   [Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a]   n [G 2 ] o [R 3 Y 2 ] p    
 
       wherein:
 each occurrence of G 1  is independently selected from a polyvalent hydrocarbon-containing species having from 1 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of G 2  is independently selected from a polyvalent hydrocarbon-containing species of 1 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of R 1  and R 3  is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms; 
 each occurrence of Y 1  and Y 2  is independently selected from the group consisting of silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of R 2  is a chemical bond or a straight chain hydrocarbon represented by —(CH 2 ) f —; 
 each occurrence of R 4  is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms said fragment possessing a cyclic structure selected from the group consisting of bicyclic, tricyclic, higher cyclic structures, and cyclic structures substituted with alkyl, alkenyl and/or alkynyl groups; 
 each occurrence of R 5  is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms said fragment possessing a cyclic structure selected from the group consisting of bicyclic, tricyclic, higher cyclic structures, and cyclic structures substituted with alkyl, alkenyl and/or alkynyl groups; 
 each occurrence of X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms and possesses a cyclic structure selected from the group consisting of bicyclic, tricyclic, higher cyclic structures, and cyclic structures substituted with alkyl, alkenyl and/or alkynyl groups; 
 each occurrence of X 2  and X 3  is independently selected from the group consisting of hydrogen, R 6 , X 1 , wherein X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms and possesses a cyclic structure selected from the group consisting of bicyclic, tricyclic, higher cyclic structures, and cyclic structures substituted with alkyl, alkenyl and/or alkynyl groups, and —OSi containing groups that result from the condensation of silanols; and, 
 each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given wherein a, c and e are 1 to about 3; b is 1 to about 5; d is 1 to about 5; f is 1 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10. 
 
     
     
       5. The silated core polysulfide of  claim 4  wherein the value of x is from 2 to 4. 
     
     
       6. A silated core polysulfide of the general formula
   [Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p    
 
       wherein:
 each occurrence of G 1  is independently selected from a polyvalent hydrocarbon-containing species derived from nonconjugated diolefins, and having from 5 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of G 2  is independently selected from a polyvalent hydrocarbon-containing species of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of R 1  and R 3  is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms; 
 each occurrence of Y 1  and Y 2  is independently selected from the group consisting of silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of R 2  is a chemical bond or a straight chain hydrocarbon represented by —(CH 2 ) f —; 
 each occurrence of R 4  is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms; 
 each occurrence of R 5  is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms; 
 each occurrence of X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of X 2  and X 3  is independently selected from the group consisting of hydrogen, R 6 , wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, X 1 , wherein X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and —OSi containing groups that result from the condensation of silanols; and, 
 each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given wherein a, c and e are 1 to about 3; b is 1 to about 5; d is about 1 to 5; f is 1 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10. 
 
     
     
       7. The silated core polysulfide of  claim 6  wherein G 1  is selected from the group consisting of —CH 2 (CH 2 ) q+1 CH(CH 2 —)— and —CH(CH 3 )(CH 2 ) q CH(CH 2 —) 2 , wherein q is zero to 20. 
     
     
       8. The silated core polysulfide of  claim 6  wherein G 1  is —CH(CH 2 )(CH 2 ) q CH(CH 2 —)—, in which q is from 1 to 20. 
     
     
       9. The silated core polysulfide of  claim 6  wherein the value of x is from 2 to 4. 
     
     
       10. A silated core polysulfide selected from the group consisting of 2-triethoxysilyl-1,3-bis-(3-triethoxysilyl-1-propyltetrathia)propane, 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-diethoxymethylsilyl-1-ethyl)-1,2-bis-(13-triethoxysilyl-3,4,5,6-tetrathiamidecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(10-triethoxysilyl-3,4,5,6,7-pentathiadecyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexane; 2-(2-triethoxysilyl-1-ethyl)-1-(7-triethoxysilyl-3,4-dithiaheptyl)-2-(8-triethoxysilyl-3,4,5-trithiaoctyl)cyclohexane; 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)benzene; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]tetrasulfide; bis-[2-(4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]disulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]disulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl tetrasulfide; bis-[2-[4-(2-triethoxysilyl-1-ethyl)-2-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)phenyl]ethyl]tetrasulfide; bis-2-[4-(2-triethoxysilyl-1-ethyl)-3-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexyl]ethyl]trisulfide; bis-[2-[4-(2-diethoxymethylsilyl-1-ethyl)-2-(7-triethoxysilyl-3,4-dithiaheptyl)cyclohexyl]ethyl disulfide, and mixtures thereof. 
     
     
       11. The silated core polysulfide of  claim 10  wherein said silated core polysulfide is selected from the group consisting of 4-(2-triethoxysilyl-1-ethyl)-1,2-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane, 1-(2-triethoxysilyl-1-ethyl)-2,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane, 2-(2-triethoxysilyl-1-ethyl)-1,4-bis-(9-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane and mixtures thereof. 
     
     
       12. A silated core polysulfide of the general formula
   [Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p    
 
       wherein:
 each occurrence of G 1  is independently selected from a polyvalent hydrocarbon-containing species having from 5 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of G 2  is independently selected from a polyvalent hydrocarbon-containing species of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
   [(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ; 
 
 each occurrence of R 1  and R 3  is independently selected from a divalent hydrocarbon fragment having from 1 to about 5 carbon atoms; 
 each occurrence of Y 1  and Y 2  is independently selected from the group consisting of silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid, ester (—C(═O)OR 6 ) wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of R 2  is a chemical bond or a straight chain hydrocarbon represented by —(CH 2 ) f —; 
 each occurrence of R 4  is independently selected from a polyvalent hydrocarbon fragment of 3 to about 10 carbon atoms; 
 each occurrence of R 5  is independently selected from a polyvalent hydrocarbon fragment of 1 to about 28 carbon atoms; 
 each occurrence of X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms; 
 each occurrence of X 2  and X 3  is independently selected from the group consisting of hydrogen, R 6 , wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, X 1 , wherein X 1  is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6  is a monovalent hydrocarbon group having from 1 to 20 carbon atoms, and —OSi containing groups that result from the condensation of silanols; and; 
 each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given wherein a, c and e are 1 to about 3; b is 1 to about 5; d is 1 to about 5; f is 1 to about 5; in and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to about 10. 
 
     
     
       13. The silated core polysulfide of  claim 12  wherein the value of x is from 2 to 4. 
     
     
       14. The silated core polysulfide of  claim 12  wherein R 1  and R 3  are branched and/or straight chain alkyl, alkenyl or alkynyl groups in which one hydrogen atom is substituted with a Y 1  or Y 2  group. 
     
     
       15. The silated core polysulfide of  claim 12  wherein Y 1  and Y 2  are silyl (—SiX 1 X 2 X 3 ), hydrogen, carboxylic acid, or ester (—C(═O)OR 6 ) wherein R 6  is a monovalent hydrocarbon group having from 1 to 5 carbon atoms. 
     
     
       16. The silated core polysulfide of  claim 12  wherein R 2  is a straight chain hydrocarbon represented by —(CH 2 ) f — where f is an integer from 1 to about 3. 
     
     
       17. The silated core polysulfide of  claim 12  wherein R 5  is a polyvalent hydrocarbon fragment of 3 to about 10 carbon atoms. 
     
     
       18. The silated core polysulfide of  claim 12  wherein X 1  is independently selected from the group consisting of hydrolysable —OH, and —OR 6 , wherein R 6  is a monovalent hydrocarbon group having from 1 to 5 carbon atoms. 
     
     
       19. The silated core polysulfide of  claim 12  wherein X 2  and X 3  are independently selected from the group consisting of R 6 , wherein R 6  is a monovalent hydrocarbon group having from 1 to 5 carbon atoms, X 1 , wherein X 1  is independently selected from the group consisting of hydrolysable —OH, —OR 6 , and —OSi containing groups that result from the condensation of silanols. 
     
     
       20. The silated core polysulfide of  claim 12  wherein each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given by a is 1 to about 2; b and d are 1 to about 3; c and e are 1; f is 1 to about 3; m and p are 1, n is 1 to about 10; o is 0 to about 1; and x is 1 to about 4.